Catalyst system composed of metallocenes comprising substituents containing fluorine

ABSTRACT

The invention relates to a catalyst system composed of metallocenes comprising substituents containing fluorine, a method for producing said system and its use for the polymerization of olefins.

The present invention relates to a catalyst system comprisingmetallocenes having fluorine-containing substituents, a process forpreparing it and its use for the polymerization of olefins.

One of the first reactions in which a metallocene of transition group IVcontaining fluorine-containing ligands is reacted is the flash pyrolysisof Cp₂Ti(C₆F₅)₂ (J. Organomet. Chem. 1963, 1, 98; J. Organomet. Chem.1964, 2, 206). Here, migration of a fluorine atom occurs.

Perfluorinated ligands play an important role in the stabilization ofelectron-deficient metal centers. For example, cationic metallocenes arestabilized in the Ziegler-Natta polymerization by perfluorinatedtetraphenylborates (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41,1220).

An electron-deficient metal center can also be stabilized by means of apartially fluorinated anion in the reaction of dimethylzirconocenecompounds with [PhMe₂NH]⁺[B(C₆H₄F)₄]⁻ (Organometallics 1991, 10, 3910).The coordination of an F atom of the anion to the metal center can beconfirmed by means of ¹⁹F-NMR spectroscopy.

The reaction of butadiene(zirconocene) with the Lewis acid B(C₆F₅)₃gives a betaine in which the cationic metal center is stabilized bycoordination of a fluorine atom of the pentafluorophenyl radical (Angew.Chem. 1995, 107, 1867). In this case, the coordination is only weak, sothat the labile ligand can be displaced by monomers.

The compounds mentioned up to now describe interactions of cationicmetallocenes with aromatic fluorine-containing ligands. The use ofpartially fluorinated or perfluorinated aliphatic substituents oncyclopentadienyl ligands of the metallocenes has only been described inisolated cases.

Thus, a titanocene in which a trifluoromethyl group is bound to acyclopentadienyl ligand is known (JACS 1986, 108, 4228).

Intramolecular coordination of a fluorine atom to the metal center ishardly possible here because of the geometry.

It is an object of the present invention to provide a catalyst systemcomprising metallocenes having fluorine-containing substituents.

We have found that this object is achieved by a catalyst system whichcomprises at least one metallocene having fluorine-containingsubstituents and at least one cocatalyst component and may be supported,and by a process for preparing it and its use in the polymerization ofpropylene.

The catalyst system of the present invention comprises

(a) at least one cocatalyst,

(b) at least one organometallic compound of the formula (I)

where

M¹ is a metal of group 3, 4, 5 or 6 of the Periodic Table of theElements or a lanthanide or actinide,

R¹ are identical or different and are each a hydrogen atom, a C₁-C₃₀group such as C₁-C₂₅-alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexylor octyl, C₂-C₂₅-alkenyl, C₃-C₁₅-alkylalkenyl, C₆-C₂₄-aryl,C₅-C₂₄-heteroaryl such as pyridyl, furyl or quinolyl, C₇-C₃₀-arylalkyl,C₇-C₃₀-alkylaryl, C₁-C₁₂-alkoxy, SiR³, where R³ are identical ordifferent and are each a hydrogen atom or a C₁-C₄₀ group such asC₁-C₂₀-alkyl, C₁-C₁₀-fluoroalkyl, C₁-C₁₀-alkoxy, C₆-C₂₀-aryl,C₆-C₁₀-fluoroaryl, C₆-C₁₀-aryloxy, C₂-C₁₀-alkenyl, C₇-C₄₀-arylalkyl,C₇-C₄₀-alkylaryl or C₈-C₄₀-arylalkenyl, or two or more radicals R¹ maybe joined to one another in such a way that the radicals R¹ and theatoms of the cyclopentadienyl ring which connect them form a C₄-C₂₄ ringsystem which may in turn be substituted,

R² are identical or different and are each fluorine-containingC₁-C₂₅-alkyl, fluorine-containing C₁-C₂₅-alkenyl, fluorine-containingC₆-C₂₄-aryl, fluorine-containing C₇-C₃₀-arylalkyl or fluorine-containingC₇-C₃₀-alkylaryl,

r, n are identical or different and are 1, 2, 3, 4 or 5,

m, q are identical or different and are 0, 1, 2, 3 or 4,

q+r is 5 when v=0, and q+r is 4 when v=1,

m+n is 5 when v=0, and m+n is 4 when v=1,

s, t are identical or different and are each an integer from 1 to 20,

L are identical or different and are each a halogen atom or ahydrocarbon-containing radical having 1-20 carbon atoms, e.g.C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₂₀-alkoxy, C₆-C₁₄-aryloxy orC₆-C₄₀-aryl,

x is an integer from 1 to 4, with x preferably being 2 when M¹=Ti, Zr orHf,

Z is a bridging structural element between the two cyclopentadienylrings, and v is 0 or 1,

and, if desired,

(c) at least one support.

Z is particularly preferably an M²R⁴R⁵ group, where M² is carbon,silicon, germanium or tin and R⁴ and R⁵ are identical or different andare each a C₁ -C₂₀-hydrocarbon group such as C₁-C₁₀-alkyl orC₆-C₁₄-aryl.

Z is preferably CH₂, CH₂CH₂, CH(CH₃)CH₂, CH(C₄H₉)C(CH₃)₂, C(CH₃)₂,(CH₃)₂Si, (CH₃CH₂)₂Si, (CH₃)((CH₃)₃C)Si, (CH₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si,(C₆H₅)(CH₃)Si, (C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Si, CH₂Si(CH₃)₂, o-C₆H₄ or2,2′-(C₆H₄)₂. It is also possible for Z together with one or moreradicals R¹ and/or R² to form a monocyclic or polycyclic ring system.

Preference is given to chiral bridged metallocenes of the formula 1, inparticular ones in which v is 1 and one or both cyclopentadienyl ringsare substituted in such a way that they form an indenyl ring. Theindenyl ring is preferably substituted, in particular in the 2 position,4 position, 2,4,5 positions, 2,4,6 positions, 2,4,7 positions or 2,4,5,6positions, by C₁-C₂₀ groups such as C₁-C₁₀-alkyl or C₆-C₂₀-aryl, wheretwo or more substituents of the indenyl ring can also together form aring system.

In formula (I), it is particularly preferred that

M¹ is a metal of group 4 of the Periodic Table of the Elements, e.g. Ti,Zr or Hf,

R¹ are identical or different and are each a hydrogen atom, a C₁-C₃₀group such as C₁-C₂₅-alkyl, in particular methyl, ethyl, tert-butyl,cyclohexyl or octyl, C₂-C₂₅-alkenyl, C₃-C₁₅-alkylalkenyl, C₆-C₂₄-aryl,C₅-C₂₄-heteroaryl such as pyridyl, furyl or quinolyl, C₇-C₃₀-arylalkyl,C₇-C₃₀-alkylaryl or C₁-C₁₂-alkoxy, SiR³, where R³ are identical ordifferent and are each a hydrogen atom or a C₁-C₄₀ group such asC₁-C₂₀-alkyl, C₁-C₁₀-fluoroalkyl, C₁-C₁₀-alkoxy, C₆-C₂₀-aryl,C₆-C₁₀-fluoroaryl, C₆-C₁₀-aryloxy, C₂-C₁₀-alkenyl, C₇-C₄₀-arylalkyl,C₇-C₄₀-alkylaryl or C₈-C₄₀-arylalkenyl, or two or more radicals R¹ maybe joined to one another in such a way that the radicals R¹ and theatoms of the cyclopentadienyl ring which connect them form a C₄-C₂₄ ringsystem which may in turn be substituted,

R² are identical or different and are each fluorine-containingC₁-C₂₅-alkyl, fluorine-containing C₁-C₂₅-alkenyl, fluorine-containingC₆-C₂₄-aryl, fluorine-containing C₇-C₃₀-arylalkyl or fluorine-containingC₇-C₃₀-alkylaryl,

r, n are identical or different and are 1, 2, 3, 4 or 5,

m, q are identical or different and are 0, 1, 2, 3 or 4,

q+r is 5 when v=0, and q+r is 4 when v=1,

m+n is 5 when v=0, and m+n is 4 when v=1,

s, t are identical or different and are each an integer from 1 to 20,

L are identical or different and are each a halogen atom or ahydrocarbon-containing radical having 1-20 carbon atoms, in particularC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₂₀-alkoxy, C₆-C₁₄-aryloxy orC₆-C₄₀-aryl,

x is an integer from 1 to 4, with x preferably being 2 when M¹=Ti, Zr orHf

Z is a bridging structural element between the two cyclopentadienylrings, and v is 0 or 1.

Illustrative but nonlimiting examples of organometallic compounds usedaccording to the present invention are:

bis(η⁵-2′, 2′, 2′-trifluoroethyl)cyclopentadienyl)titanium dichloride

bis(η⁵-1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienyl)titaniumdichloride

bis(η⁵-1′H, 1′H, 2′H, 2′H-perfluorohexylcyclopentadienyl)titaniumdichloride

bis(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)titanium dichloride

bis(η⁵-2′, 2′, 2′-trifluoroethyl)cyclopentadienyl)zirconium dichloride

bis(η⁵-1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienyl)zirconiumdichloride

bis(η⁵-1′H, 1′H, 2′H, 2′H-perfluorohexylcyclopentadienyl)zirconiumdichloride

bis(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)zirconium dichloride

bis(η⁵-2′, 2′, 2′-trifluoroethyl)cyclopentadienyl)hafnium dichloride

bis(η⁵-1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienyl)hafniumdichloride

bis(η⁵-1′H, 1′H, 2′H, 2′H-perfluorohexylcyclopentadienyl)hafniumdichloride

bis(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)hafnium dichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)titaniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-cyclopentadienyl)titaniumdichloride

(η⁵-1′H, 1′H, 2′H, 2′H-perfluorohexylcyclopentadienyl)(η⁵-cyclopentadienyl)titanium dichloride

(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)(η⁵-cyclopentadienyl)titaniumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-cycIopentadienyl)zirconiumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorohexylcyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)hafniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(72⁵-cyclopentadienyl)hafniumdichloride

(η⁵- 1′H, 1′H, 2′H,2′H-perfluorohexylcyclopentadienyl)(η⁵-cyclopentadienyl)hafniumdichloride

(η⁵-3′-(trifluoromethyl)-3′,4′,4′,4′-tetrafluorobutylcyclopentadienyl)(η⁵-cyclopentadienyl)hafnium dichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-pentamethylcyclopentadienyl)titaniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-pentamethylcyclopentadienyl)titaniumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-pentamethylcyclopentadienyl)zirconiumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctyicyclopentadienyl)(η⁵-pentamethylcyclopentadienyl)zirconiumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-pentamethylcyclopentadienyl)hafniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-pentamethylcyclopentadienyl)hafniumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-methylcyclopentadienyl)titaniumdichloride

(η⁵-1l′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-methylcyclopentadienyl)titaniumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-methylcyclopentadienyl)zirconiumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-methylcyclopentadienyl)zirconiumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-methylcyclopentadienyl)hafniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-methylcyclopentadienyl)hafniumdichloride

dimethylsilanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)titaniumdichloride

dimethylsilanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)titaniumdichloride

dimethylsilanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)zirconiumdichloride

dimethylsilanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)zirconiumdichloride

dimethylsilanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)hafniumdichloride

dimethylsilanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)hafniumdichloride

dimethylsilanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)titaniumdichloride

dimethylsilanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-cyclopentadienyl)titaniumdichloride

dimethylsilanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

dimethylsilanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

dimethylsilanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)hafniumdichloride

dimethylsilanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-cyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3- (2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H, 2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)hafnium dichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η5-3-methylcyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η5-3-methylcyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3- (2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η5-cyclopentadienyl)titaniumdichloride

1,2-ethanediyI(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-cyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-cyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-cyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-methylcyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)titaniumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)zirconiumdichloride

1,2-ethanediyl(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)hafniumdichloride

1,2-ethanediyl(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(η⁵-3-butylcyclopentadienyl)hafniumdichloride

dimethylsilanediylbis(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)zirconium dichloride

dimethylsilanediylbis(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)titanium dichloride

dimethylsilanediylbis(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)titanium dichloride

dimethylsilanediylbis(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)zirconium dichloride

dimethylsilanediylbis(η⁵-3-(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)hafnium dichloride

dimethylsilanediylbis(η⁵-3-(1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)hafnium dichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-butylcyclopentadienyl)titaniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-butylcyclopentadienyl)titaniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorohexylcyclopentadienyl)(η⁵-butylcyclopentadienyl)titaniumdichloride

(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)(η ⁵-butylcyclopentadienyl)titaniumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-butylcyclopentadienyl)zirconiumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-butylcyclopentadienyl)zirconiumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorohexylcyclopentadienyl)(η⁵-butylcyclopentadienyl)zirconiumdichloride

(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)(η⁵-butylcyclopentadienyl)zirconiumdichloride

(η⁵-2′, 2′,2′-trifluoroethyl)cyclopentadienyl)(η⁵-butylcyclopentadienyl)hafniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(η⁵-butylcyclopentadienyl)hafniumdichloride

(η⁵-1′H, 1′H, 2′H,2′H-perfluorohexylcyclopentadienyl)(η⁵-butylcyclopentadienyl)hafniumdichloride

(η⁵-3′-(trifluoromethyl)-3′, 4′, 4′,4′-tetrafluorobutylcyclopentadienyl)(η⁵-butylcyclopentadienyl)hafniumdichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)benzoindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′, 2′-trifluoroethyl)indenyl)zirconiumdichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)-4-(1-naphthyl)indenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)-4-(2-naphthyl)indenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)-4-phenylindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)-4-phenylindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)-4,5-benzoindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(2′, 2′,2′-trifluoroethyl)-4-(4′-tert-butylphenyl)indenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H, 2′H-perfluorooctyl)benzoindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)indenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)-4-(1-naphthyl)indenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)-4-(2-naphthyl)indenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)-4-phenylindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)-4-phenylindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)-4,5-benzoindenyl)zirconium dichloride

dimethylsilanediylbis(η⁵-2-(1′H, 1′H, 2′H,2′H-perfluorooctyl)-4-(4′-tert-butylphenyl)indenyl)zirconium dichloride

Apart from the dichloride compounds, the dimethyl compounds are also ofimportance.

The compound of the formula (I) is prepared by reacting a substitutedcyclopentadienide (II) obtained from the reaction of a metallocene witha fluorine- and iodine-containing alkyl with a metal compound (Ill);this is illustrated by way of example in the following reaction scheme.

In this scheme, M¹, R¹, R², L, Z, m, n, q, r, s, t, v and x are asdefined above for formula (I). y is 1 or 2 and M is a metal,particularly preferably nickel. The base is a strong base such asbutyllithium or potassium hydride. The reaction is carried out at from−50° C. to +150° C., preferably from 0°C. to 100° C., in organicsolvents such as toluene, benzene, methylene chloride, carbontetrachloride, tetrahydrofuran, diethyl ether or petroleum spirit. Thereaction takes from 1 minute to 20 days. The compound of the formula (I)can be isolated or used directly for further reactions. The compound ofthe formula (I) can also be prepared in a single-vessel reaction withoutisolation of intermediates and end products.

In addition to at least one metallocene of the formula (I), the catalystsystem of the present invention further comprises at least onecocatalyst (component a).

The cocatalyst component comprises an aluminoxane, a Lewis acid or anionic compound which reacts with the metallocene to convert it into acationic compound.

As aluminoxane, preference is given to using a compound of the formula(IV)

(R AlO)p   (IV).

Aluminoxanes can be cyclic as in formula (V)

or linear as in formula (VI)

or of the cluster type as in formula (VII), as are described in recentliterature, cf. JACS 117 (1995), 6465-74, Organometallics 13 (1994),2957-2969.

The radicals R in the formulae (V), (VI) and (VII) can be identical ordifferent and may each be a C₁-C₂₀-hydrocarbon group such as aC₁-C₆-alkyl group, a C₆-C₁₈-aryl group, benzyl or hydrogen, and p is aninteger from 2 to 50, preferably from 10 to 35.

The radicals R are preferably identical and are methyl, isobutyl,n-butyl, phenyl or benzyl, particularly preferably methyl.

If the radicals R are different, they are preferably methyl andhydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen orisobutyl or n-butyl preferably being present in a proportion of from0.01 to 40% (number of radicals R).

Aluminoxanes are prepared as described in the literature (cf. Polyhedron9 (1990) 429 and EP-A-302 424).

Regardless of the method of preparation, all aluminoxane solutions havea varying content of unreacted aluminum starting compound which ispresent in free form or as adduct.

As Lewis acid, preference is given to using at least one organoboron ororganoaluminum compound containing C₁-C₂₀ groups such as branched orunbranched alkyl or haloalkyl groups, e.g. methyl, propyl, isopropyl,isobutyl or trifluoromethyl, unsaturated groups such as aryl orhaloaryl, e.g. phenyl, tolyl, benzyl, p-fluorophenyl,3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl,3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl.

Examples of Lewis acids are trifluoroborane, tris(4-fluorophenyl)borane,

tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane,

tris(pentafluorophenyl)borane, tris(3,5-difluorophenyl)borane and/or

tris(3,4,5-trifluorophenyl)borane, di(bis(pentafluorophenyl)boroxy)methylalane,

di(bisphenylboroxy)methylalane,di(bis(pentafluorophenyl)boroxy)isopropylalane.

As ionic cocatalysts, preference is given to using compounds whichcontain a noncoordinating anion such astetrakis(pentafluorophenyl)borate, tetraphenylborate, SbF₆—, CF₃SO₃— orClO₄ ⁻. As cationic counterion, use is made of Lewis bases such asmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, N,N-dimethylaniline, trimethylamine, triethylamine,tri-n-butylamine, methyidiphenylamine, pyridine,p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,triethylphosphine, triphenylphosphine, diphenylphosphine,tetrahydrothiophene and triphenylcarbenium.

Examples of such ionic compounds which can be used according to thepresent invention are

tributylammonium tetra(pentafluorophenyl)borate,

tributylammonium tetra(pentafluorophenyl)aluminate,

tributylammonium tetra(trifluoromethylphenyl)borate,

tributylammonium tetra(4-fluorophenyl)aborate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate,

di(propyl)ammonium tetrakis(pentafluorophenyl)borate,

di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate,

triphenylcarbenium tetrakis(pentafluorophenyl)borate,

triphenylcarbenium tetrakis(pentafluorophenyl)aluminate,

ferrocenium tetrakis(pentafluorophenyl)borate and/or

ferrocenium tetrakis(pentafluorophenyl)aluminate.

Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl)borate and/or

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

It is also possible to use mixtures of at least one Lewis acid and atleast one ionic compound.

The catalyst system of the present invention may further comprise asupport (component c). The support can be any organic or inorganic,inert solid, in particular a porous support such as talc, inorganicoxides and finely divided polymer powders such as polyolefins. Suitableinorganic oxides are, for example, silicon dioxide, aluminum oxide andalso mixed oxides of the two elements and corresponding oxide mixtures.

The support materials used have a specific surface area in the rangefrom 10 m²/g to 1000 m²/g, a pore volume in the range from 0.1 ml/g to 5ml/g and a mean particle size of from 1 μm to 500 μm. Preference isgiven to supports having a specific surface area in the range from 50 μmto 500 μm, a pore volume in the range from 0.5 ml/g to 3.5 ml/g and amean particle size in the range from 5 μm to 350 μm. Particularpreference is given to supports having a specific surface area in therange from 200 m²/g to 400 m²/g, a pore volume in the range from 0.8ml/g to 3.0 ml/g and a mean particle size of from 10 μm to 200 μm.

If the support material used naturally has a low moisture content orresidual solvent content, dehydration or drying before use can beomitted. If this is not the case, as when using silica gel as supportmaterial, dehydration or drying is advisable. The loss on ignition (LOI)should be 1% or less. The thermal dehydration or drying of the supportmaterial can be carried out under reduced pressure with simultaneousblanketing with inert gas, e.g. nitrogen. The drying temperature is inthe range from 100° C. to 1000° C., preferably from 200° C. to 800° C.The parameter pressure is not critical in this case. The duration of thedrying process can be from 1 to 24 hours. Shorter or longer drying timesare possible, provided that establishment of equilibrium with thehydroxyl groups on the support surface can occur under the conditionschosen, which normally takes from 4 to 8 hours.

Dehydration or drying of the support material by chemical means is alsopossible, by reacting the adsorbed water and the hydroxyl groups on thesurface with suitable modifying agents. The reaction with the modifyingagent can convert all or some of the hydroxyl groups into a form whichleads to no adverse interaction with the catalytically active centers.Suitable modifying agents are, for example, silicon halides and silanes,e.g. silicon tetrachloride, chlorotrimethylsilane,dimethylaminochlorosilane, amines such as phenyldimethylamine, pyridineor organometallic compounds of aluminum, boron and magnesium, e.g.trimethylaluminum, triethylaluminum, triisobutylaluminum,triethylborane, dibutylmagnesium. Chemical dehydration or modificationof the support material can be carried out by reacting a suspension ofthe support material in a suitable solvent in the absence of air andmoisture with the modifying agent in pure form or as a solution in asuitable solvent. Suitable solvents are aliphatic or aromatichydrocarbons such as pentane, hexane, heptane, toluene or xylene.Modification is carried out at from 250° C. to 120° C., preferably from50° C. to 70° C. Higher and lower temperatures are possible. Theduration of the reaction is from 30 minutes to 20 hours, preferably from1 to 5 hours. After chemical dehydration is complete, the supportmaterial is isolated by filtration under inert conditions, washed one ormore times with suitable inert solvents as have been described above andsubsequently dried in a stream of inert gas or under reduced pressure.

Organic support materials such as finely divided polyolefin powders,e.g. polyethylene, polypropylene or polystyrene, can also be used andshould likewise be freed of adhering moisture, solvent residues or otherimpurities before use by means of appropriate purification and dryingoperations.

To prepare the supported catalyst system, at least one of theabove-described metallocene components, at least one cocatalystcomponent and at least one support material are brought into contact inany order in a suitable solvent. The solvent is removed and theresulting supported metallocene catalyst system is dried to ensure thatthe solvent is completely or mostly removed from the pores of thesupport material. The supported catalyst is obtained as a free-flowingpowder.

Examples of suitable solvents include alkanes such as pentane,isopentane, hexane, heptane, octane and nonane, cycloalkanes such ascyclopentane and cyclohexane, and aromatics such as benzene, toluene,ethylbenzene and diethylbenzene. Very particular preference is given totoluene.

The amounts of cocatalyst and metallocene used in the preparation of thesupported catalyst system can be varied over a wide range. Preference isgiven to a molar ratio of cocatalyst to the transition metal in themetallocene of from 1:1 to 1000:1, very particularly preferably from 1:1to 400:1.

The supported catalyst system prepared according to the presentinvention can either be used directly for the polymerization of olefinsor be prepolymerized with one or more olefinic monomers before it isused in a polymerization process. The procedure for theprepolymerization of supported catalyst systems is described in WO94/28034.

As additive, it is possible to add a small amount of an α-olefin such asstyrene as activity-promoting component or of an antistatic, asdescribed in U.S. Ser. No. 08/365,280, during or after the preparationof the supported catalyst system.

In addition, the present invention provides a process for preparingpolyolefins by polymerization of olefins in the presence of the catalystsystem of the present invention. The polymerization can be ahomopolymerization or a copolymerization.

For the purposes of the present invention, polyolefins are polymersbased on olefins of the formula R^(α)—CH═CH—R^(β), where R^(α) and R^(β)are identical or different and are each a hydrogen atom, a halogen atom,an alkoxy, hydroxy, alkylhydroxy, aldehyde, carbonyl, carboxyl orcarboxylic ester group or a saturated or unsaturated hydrocarbon radicalhaving from 1 to 20 carbon atoms, in particular from 1 to 10 carbonatoms, which may be substituted by an alkoxy, hydroxy, alkylhydroxy,aldehyde, carbonyl, carboxyl or carboxylic ester group, or R^(α) andR^(β) together with the atoms connecting them form one or more rings.

Examples of such olefins are 1 -olefins such as ethene, propylene,1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene,dienes such as 1,3-butadiene, 1,4-hexadiene, vinylnorbornene,norbornadiene or ethylnorbornadiene and cyclic olefins such asnorbornene, tetracyclododecene or methylnorbornene.

It is also possible to copolymerize mixtures of the above olefins. Inparticular, propylene is homopolymerized or copolymerized.

The polymerization is preferably carried out at from −60 to 300° C.,particularly preferably from 30 to 250° C. The pressure is from 0.5 to2500 bar, preferably from 2 to 1500 bar.

The polymerization can be carried out continuously or batchwise, in oneor more stages, in solution, in suspension, in the gas phase or in asupercritical medium. The supported system can be resuspended as powderor while still moist with solvent and be metered as a suspension in aninert suspension medium into the polymerization system.

A prepolymerization can be carried out with the aid of the catalyst ofthe present invention. Prepolymerization is preferably carried out usingthe propylene used in the polymerization.

To prepare polypropylene having a broad molecular weight distribution,preference is given to using catalyst systems which comprise two or moredifferent metallocenes.

To remove catalyst poisons present in the olefin, purification using analuminum alkyl, for example trimethylaluminum, triethylaluminum ortriisobutylaluminum, is advantageous. This purification can either becarried out in the polymerization system itself or the olefin is broughtinto contact with the Al compound and subsequently separated off againbefore it is introduced into the polymerization system.

As molar mass regulator and/or to increase the activity, hydrogen isadded if necessary. The total pressure in the polymerization system isfrom 0.5 to 2500 bar, preferably from 2 to 1500 bar.

The compound used according to the present invention is employed in aconcentration, based on the transition metal, of preferably from 10⁻³ to10⁻⁸ mol, preferably from 10⁻⁴ to 10⁻⁷ mol, of transition metal per dm³of solvent or per dm³ of reactor volume.

Before addition of the catalyst system (comprising at least onemetallocene according to the present invention), another alkylaluminumcompound such as trimethylaluminum, triethylaluminum,triisobutylaluminum, trioctylaluminum or isoprenylaluminum canadditionally be introduced into the reactor or added to the catalystsystem to make the polymerization system inert (for example, to removecatalyst poisons present in the olefin). This additional alkylaluminumcompound is added to the polymerization system in a concentration offrom 100 to 0.01 mmol of Al per kg of reactor contents. Preference isgiven to using triisobutylaluminum and triethylaluminum in aconcentration of from 10 to 0.1 mmol of Al per kg of reactor contents.This allows a small Al/M molar ratio to be used in the synthesis of asupported catalyst system.

EXAMPLE 1

Synthesis of bis(2′, 2′, 2′-trifluoroethylcyclopentadienyl)titaniumdichloride

Synthesis of nickelocene

29.4 g of nickel powder are suspended in 400 ml of dimethoxyethane andadmixed while stirring with 27.3 ml of bromine. The mixture is stirredfor 1 hour and the solvent is removed in an oil pump vacuum. The brownresidue obtained is taken up in 400 ml of diethylamine while cooling inice and admixed with 98 ml of freshly distilled cyclopentadiene. Thesuspension becomes green. After stirring for 12 hours at roomtemperature, residual solvent is removed in an oil pump vacuum and theproduct is isolated by Soxhlet extraction with 700 ml of petroleumether.

Yield: 74g (78%)

Melting point: 173.0° C.

Synthesis of 2′, 2′, 2′-trifluoroethylcyclopentadiene

6.87 g of nickelocene and 9.51 g of triphenylphosphine are dissolved in60 ml of diethyl ether and admixed with 3.56 ml of 2,2,2-trifluoroethyliodide. The solution becomes violet and is stirred for 48 hours. Thecontents of the Schlenk vessel are then condensed into a receiver cooledto −196° C. and the diethyl ether is distilled from this at a bathtemperature of 45° C. until the temperature of the distillate is nolonger 35° C.; the proportion of remaining diethyl ether is determinedby means of ¹H-NMR (1.95 eq).

Yield: 8.95 g (81%).

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.46 (m, 6H, ═CH); 3.15 (m,4H, CH₂); 3.00 (m, 4H, CH₂ (ring), (the product consists of two doublebond isomers)) ppm.

(The resonances of the diethyl ether present appear in addition: 3.45(q); 1.18 (t) ppm).

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−65.7 (t, ³J_(HF)=11.4 Hz);−65.9 (t, ³J_(HF)=11.5 Hz) ppm.

Synthesis of bis(2′, 2′, 2′-trifluoroethylcyclopentadienyl)titaniumdichloride

14.6 mmol of 2′, 2′, 2′-trifluoroethylcyclopentadiene in tetrahydrofuranare admixed at −78° C. with 8.8 ml of 1.65 M butyllithium solution. Inparallel thereto, 0.72 ml of titanium tetrachloride are dissolved in 50ml of toluene and, at −78° C., slowly admixed with 40 ml oftetrahydrofuran. The suspension obtained is added to the above solutionat −78° C. The mixture is allowed to warm slowly to room temperature,the solvent is removed in an oil pump vacuum and the product isextracted from the residue with methylene chloride.

Yield: 1g (37%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.91 (pt, 4H, RCpH); 5.28 (pt,4H, RCpH); 3.52 (q, ³J_(FH)=11.0 Hz, 4H, 1′-H) ppm.

¹⁹F-NMR: (d₆-benzene; 284.1 MHz; 300K): δ=−65.17 (s (1H decoupled)); (t,³J_(HF)=11.5 HZ) (not decoupled)) ppm.

EXAMPLE 2

Synthesis of bis(2′, 2′, 2′-trifluoroethylcyclopentadienyl)zirconiumdichloride

11.7 mmol of 2′, 2′, 2′-trifluoroethylcyclopentadiene from Example 1 in80 ml of tetrahydrofuran are admixed at −78° C. with 7.1 ml of 1.65 Mbutyllithium solution in hexane. At −78° C., 2.22 g of zirconiumtetrachloride-THF adduct dissolved in 30 ml of tetrahydrofuran are addedto the resulting solution. The mixture is allowed to warm slowly to roomtemperature, the solvent is removed in an oil pump vacuum and theproduct is extracted from the residue with methylene chloride. Yield:1.89 g (70%)

¹H-NMR: (d₆-benzene; 300.1 MHz; 300 K): δ=5.82 (pt, 4H, RCpH); 5.39 (pt,4H, RCpH); 3.24 (q, ³J_(FH)=12.5 Hz, 4H, 1′-H) ppm.

¹⁹F-NMR: (d₆-benzene; 284.1 MHz; 300K): δ=−65.14 (s (¹H decoupled)); (t,³J_(HF)=11.5 Hz) (not decoupled)) ppm.

EXAMPLE 3

Synthesis of (2′, 2′,2′-trifluoroethylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride

1.8 mmol of 2′, 2′, 2′-trifluoroethylcyclopentadiene from Example 1 intetrahydrofuran are admixed at −78° C. with 1.05 ml of 1.65 Mbutyllithium solution. A cooled suspension of 0.46 g ofcyclopentadienylzirconium trichloride in 50 ml of tetrahydrofuran isadded thereto. The mixture is allowed to warm slowly to roomtemperature, the solvent is removed in an oil pump vacuum and theproduct is extracted from the residue with methylene chloride.

Yield: 0.47 g (70%)

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.49 (s, 5H, CpH); 6.38 (m,4H, RCpH); 3.46 (q, ³J_(FH)=10.8 Hz, 2H, 1′-H) ppm.

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−66.03 (s (¹H decoupled));(t, ³J_(HF)=11.5 Hz) (not decoupled)) ppm.

EXAMPLE 4

Synthesis of bis(2′, 2′, 2′-trifluoroethylcyclopentadienyl)hafniumdichloride

5.18 mmol of 2′, 2′, 2′-trifluoroethylcyclopentadiene from Example 1 areadmixed at −78° C. with 3.14 ml of 1.65 M butyllithium solution inhexane. 0.8 g of hafnium tetrachloride is added to the resultingsolution at −78° C. The mixture is allowed to warm slowly to roomtemperature, the solvent is removed in an oil pump vacuum and theproduct is extracted from the residue with methylene chloride. Yield:1.79 g (64%)

¹H-NMR: (d₆-benzene; 300.1 MHz; 300 K): δ=5.73 (pt, 4H, RCpH); 5.31 (pt,4H, RCpH); 3.24 (q, ³J_(FH)=10.8 HZ, 4H, 1′-H) ppm.

¹⁹F-NMR: (d₆-benzene; 282.4 MHz; 300K): δ=−65.8 (s (¹H decoupled)); (t,³J_(HF)=11.5 HZ) (not decoupled)) ppm.

EXAMPLE 5

Synthesis of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)titanium dichloride

Synthesis of 1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadiene

2.29 g of nickelocene from Example 1 and 3.17 g of triphenylphosphineare dissolved in 5 ml of diethyl ether and admixed with 3.0 ml of 1 H, 1H, 2H, 2H-perfluorooctyl iodide. The solution becomes violet and isstirred for 48 hours. The supernatant solution is subsequently filtered,the precipitate is carefully washed and the solvent is then removed. Theresidue is chromatographed on a short column using pentane and thesolvent is removed in an oil pump vacuum.

Yield: 3.67 g (74%)

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.45; 6.39; 6.28; 6.22; 6.05(each m, 3H, RCpH); 2.97 (pq, (1-isomer), 2.91 (psext, (2-isomer),together 4 H, CH2); 2.67 (m, 4H, 1′-H); 2.31 (m, 4H, 2′-H) ppm.

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−81.24 (m, 3F, 8′-F);−114.77 (m, 2F, 3′-F); −122.07 (m, 2F, 4′-F); −123.06 (m, 2F, 7′-F);−123.67 (m, 2F, 6′-F) −126.37 (m, 2F, 5′F) ppm.

Synthesis of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)titanium dichloride

A solution of 0.75 g of 1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienein 40 ml of tetrahydrofuran is admixed at −78° C. with 1.04 ml of 1.65 Mbutyllithium solution and then admixed with a cooled suspension of 0.168g of titanium tetrachloride-THF adduct in 45 ml of tetrahydrofuran. Themixture is allowed to warm to room temperature and the solvent isremoved under reduced pressure. The product is isolated by means ofextraction with methylene chloride.

Yield: 0.1 g (12%)

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.39 (pt, 4H, RCpH); 6.28(pt, 4H, RCpH); 3.12 (m, 4H, 1′-H); 2.48 (m, 4H, 2′-H) ppm.

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−81.0 (m, 6F, 8′-F); −114.3(m, 4F, 3′-F); −122.1 (m, 4F, 4′-F); −123.1 (m, 4F, 7′-F); −123.6 (m,4F, 6′-F); −126.3 (m, 4F, 5′-F) ppm.

EXAMPLE 6

Synthesis of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)zirconium dichloride

A solution of 0.98 g of 1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienefrom Example 5 in 60 ml of tetrahydrofuran is admixed at −78° C. with1.49 ml of 1.65 M butyllithium solution and then admixed with a cooledsuspension of 0.426 g of zirconium tetrachloride-THF adduct in 40 ml oftetrahydrofuran. The mixture is allowed to warm to room temperature andthe solvent is removed under reduced pressure. The product is isolatedby means of extraction with methylene chloride.

Yield: 0.56 g (50%)

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.33 (pt, 4H, RCpH); 6.24(pt, 4H, RCpH); 2.98 (m, 4H, 1′-H); 2.09 (m, 4H, 2′-H) ppm.

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−81.0 (m, 6F, 8′-F); −114.5(m, 4F, 3′-F); −122.0 (m, 4F, 4′-F); −123.0 (m, 4F, 7′-F); −123.6 (m,4F, 6′-F); −126.3 (m, 4F, 5′-F) ppm.

EXAMPLE 7

Synthesis of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)hafnium dichloride

A solution of 0.87 g of 1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienefrom Example 5 in 60 ml of tetrahydrofuran is admixed at −78° C. with1.21 ml of 1.65 M butyllithium solution and then admixed with a cooledsuspension of 0.305 g of hafnium tetrachloride in 40 ml oftetrahydrofuran. The mixture is allowed to warm to room temperature andthe solvent is removed under reduced pressure. The product is isolatedby means of extraction with methylene chloride.

Yield: 0.38 g (38%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.57 (pt, 4H, RCpH); 5.47 (pt,4H, RCpH); 2.86 (m, 4H, 1′-H); 2.10 (m, 4H, 2′-H) ppm.

¹⁹F-NMR: (d₆-benzene; 282.4 MHz; 300K): δ=−81.2 (m, 6F, 8′-F); -114.5(m, 4F, 3′-F); −121.9 (m, 4F, 4′-F); −122.9 (m, 4F, 7′-F); −123.4 (m,4F, 6′-F); −126.2 (m, 4F, 5′-F) ppm.

EXAMPLE 8

Synthesis of ((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)(cyclopentadienyl)zirconiumdichloride

A solution of 1.31 g of 1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienefrom Example 5 in 25 ml of tetrahydrofuran is admixed at −78° C. with 2ml of 1.65M butyllithium solution and then admixed with a cooledsuspension of 1.28 g of cyclopentadienylzirconium trichloride-THF adductin 40 ml of tetrahydrofuran. The mixture is allowed to warm to roomtemperature and the solvent is removed under reduced pressure. Theproduct is isolated by means of extraction with methylene chloride andpentane.

Yield: 1.73g (86%)

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.47 (s, 5H, CpH); 6.32 (pt,2H, RCpH); 6.23 (pt, 2H, RCpH); 2.98 (m, 2H, 1′H); 2.38 (m, 2H, 2′H)ppm.

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−81.0 (m, 3F, 8′-F); −114.5(m, 2F, 3′-F); −122.0 (m, 2F, 4′-F); −123.0 (m, 2F, 7′-F); −123.6 (m,2F, 6′-F); −126.3 (m, 2F, 5′-F) ppm.

EXAMPLE 9

Synthesis of (1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdichloride

A solution of 1.39 g of 1′H, 1′H, 2′H, 2′H-perfluorooctylcyclopentadienefrom Example 5 in 50 ml of tetrahydrofuran is admixed at −78° C. with2.1 ml of 1.65 M butyllithium solution and then admixed with a cooledsuspension of 1.11 g of pentamethylcyclopentadienylzirconium trichloridein 30 ml of tetrahydrofuran. The mixture is allowed to warm to roomtemperature and the solvent is removed under reduced pressure. Theproduct is isolated by means of extraction with methylene chloride andpentane.

Yield: 1.9 g (81%)

¹H-NMR: (d-chloroform; 200.1 MHz; 300 K): δ=6.06 (pt, 2H, RCpH); 5.94(pt, 2H, RCpH); 3.72 (m, 2H, 1′-H); 2.97 (m, 2H, 2′-H); 2.02 (s, 15H,Cp(CH₃)₅) ppm.

¹⁹F-NMR: (d-chloroform; 282.4 MHz; 300K): δ=−80.9 (m, 3F, 8′-F); −114.5(m, 2F, 3′-F); −122.2 (m, 2F, 4′-F); −123.0 (m, 2F, 7′-F); -123.6 (m,2F, 6′-F); −126.3 (m, 2F, 5′-F) ppm.

EXAMPLE 10

Synthesis of bis(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)dimethylzirconium

2.79 ml of 1.68 M methyllithium solution in diethyl ether are addedslowly at −78° C. to a suspension of 1.05 g of bis(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)zirconium dichloride from Example 2in 40 ml of diethyl ether. The mixture is allowed to warm to roomtemperature and the solvent is removed in an oil pump vacuum. Theproduct is isolated by means of extraction with pentane. Yield: 0.614 g(73%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.62 (pt, 4H, RCpH); 5.21 (pt,4H, RCpH); 2.87 (q, ³J_(FH)=10.6 Hz, 4H, 1′-H); −0.52 (s, 6H, Zr—CH₃)ppm.

EXAMPLE 11

Synthesis of (2′, 2′,2′-trifluoroethylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium

0.8 ml of 1.68 M methyllithium solution in diethyl ether is added slowlyat −78° C. to a suspension of 0.252 g of (2′, 2′,2′-trifluoroethylcyclopentadienyl)(cyclopentadienyl)zirconium dichloridefrom Example 3 in 25 ml of diethyl ether. The mixture is allowed to warmto room temperature and the solvent is removed in an oil pump vacuum.The product is isolated by means of extraction with pentane. Yield:0.162 g (73%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.64 (s, 5H, CpH); 5.63 (pt,2H, RCpH); 5.27 (pt, 2H, RCpH); 2.87 (q, ³J_(FH)=10.8 Hz, 2H, 1′-H);−0.32 (s, 6H, Zr—(CH₃) ppm.

EXAMPLE 12

Synthesis of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)dimethylzirconium

1.04 ml of 1.68 M methyllithium solution in diethyl ether is addedslowly at −78° C. to a suspension of 0.51 g of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)titanium dichloride from Example 5in 50 ml of diethyl ether. The mixture is allowed to warm to roomtemperature and the solvent is removed in an oil pump vacuum. Theproduct is isolated by means of extraction with pentane. Yield: 0.302 g(65%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.46 (pt, 4H, RCpH); 5.37 (pt,4H, RCpH); 2.60 (m, 4H, 1′-H); 2.05 (m, 4H, 2′H); −0.29 (s, 6H, Zr—CH₃)ppm.

EXAMPLE 13

Synthesis of (1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(cyclopentadienyl)dimethylzirconium

1.03 ml of 1.68 M methyllithium solution in diethyl ether is addedslowly at −78° C. to a suspension of 0.525 g of (1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride from Example 8 in 40 ml of diethyl ether. The mixture isallowed to warm to room temperature and the solvent is removed in an oilpump vacuum. The product is isolated by means of extraction withpentane. Yield: 0.257 g (55%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.70 (s, 5H, CpH); 5.45 pt,2H, RCpH); 5.36 (pt, 2H, RCpH); 2.60 (m, 2H, 1′-H); 2.09 (m, 2H, 2′H);−0.21 (s, 6H, Zr—(CH₃)₂) ppm.

EXAMPLE 14

(1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(pentamethylcyclopentadienyl)dimethylzirconium

2.7 ml of 1.68 M methyllithium solution in diethyl ether are addedslowly at −78° C. to a suspension of 1.9 g of (1′H, 1′H, 2′H,

2′H-perfluorooctylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdichloride from Example 9 in 40 ml of diethyl ether. The mixture isallowed to warm to room temperature and the solvent is removed in an oilpump vacuum. The product is isolated by means of extraction withpentane. Yield: 1.33 g (74%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.51 (pt, 2H, RCpH); 5.28 (pt,2H, RCpH); 2.74 (m, 2H, 1′-H); 2.13 (m, 2H, 2′-H); 1.67 (s, 15H,Cp(CH₃)₅); −0.44 (s, 6H, Zr—CH₃) ppm.

EXAMPLE 15

Synthesis of bis((2′, 2′,2′-trifluoroethyl)cyclopentadienyl)dimethylhafnium

1.1 ml of 1.68 M methyllithium solution in diethyl ether is added slowlyat −78° C. to a suspension of 0.5 g of bis((2, 2′,2′-trifluoroethyl)cyclopentadienyl)hafnium dichloride from Example 4 in50 ml of diethyl ether. The mixture is allowed to warm to roomtemperature and the solvent is removed in an oil pump vacuum. Theproduct is isolated by means of extraction with pentane.

Yield: 0.358 g (83%)

¹H-NMR: (d₆-benzene; 200.1 MHz; 300 K): δ=5.52 (pt, 4H, RCpH); 5.16 (pt,4H, RCpH); 2.87 (q, ³J_(FH)=10.7 Hz, 4H, 1′-H); −0.71 (s, 6H,Hf—CH₃)ppm.

EXAMPLE 16

Synthesis of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)dimethylhafnium

0.25 ml of 1.68 M methyllithium solution in diethyl ether is addedslowly at −78° C. to a suspension of 0.222 g of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)hafnium dichloride from Example 7 in40 ml of diethyl ether. The mixture is allowed to warm to roomtemperature and the solvent is removed in an oil pump vacuum. Theproduct is isolated by means of extraction with pentane.

Yield: 0.197 g (91%)

¹H-NMR: (d6-benzene; 200.1 MHz; 300 K): δ=5.38 (pt, 4H, RCpH); 5.31 (pt,4H, RCpH); 2.59 (m, 4H, 1′-H); 2.08 (m, 4H, 2′-H); −0.47 (s, 6H, Hf—CH₃)ppm.

EXAMPLE 17

Polymerization of propene

200 ml of toluene and 19 ml of 10.5% strength methylaluminoxane solutionin toluene are placed in a 1 l glass autoclave. 1 ml of 10.5% strengthmethylaluminoxane solution in toluene and 40 mg of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)zirconium dichloride are addedthereto. The polymerization temperature of 0° C. is subsequently set andthe autoclave is pressurized with 2 bar of propene; the propene pressureis maintained during the polymerization by injection of further amounts.The polymerization is stopped by addition of 20 ml of methanol/2Nhydrochloric acid (1:1). The polypropylene obtained is filtered off anddried in an oil pump vacuum.

Activity: 33 μ(mmol·bar·h)

EXAMPLE 18

Polymerization of propene

200 ml of toluene and 19 ml of 10.5% strength methylaluminoxane solutionin toluene are placed in a 1 l glass autoclave. 1 ml of 10.5% strengthmethylaluminoxane solution in toluene and 15 mg of (1′H, 1′H, 2′H,2′H-perfluorooctylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride are added thereto. The polymerization temperature of 0° C. issubsequently set and the autoclave is pressurized with 2 bar of propene;the propene pressure is maintained during the polymerization byinjection of further amounts. The polymerization is stopped by additionof 20 ml of methanol/2N hydrochloric acid (1:1). The polypropyleneobtained is filtered off and dried in an oil pump vacuum.

Activity: 144 g/(mmol·bar·h)

EXAMPLE 19

Polymerization of ethene

200 ml of toluene and 19 ml of 10.5% strength methylaluminoxane solutionin toluene are placed in a 1 1 glass autoclave. 1 ml of 10.5% strengthmethylaluminoxane solution in toluene and 16 mg of bis(2′, 2′,2′-trifluoroethylcyclopentadienyl)zirconium dichloride are addedthereto. The polymerization temperature of 10° C. is subsequently setand the autoclave is pressurized with 2 bar of ethene; the ethenepressure is maintained during the polymerization by injection of furtheramounts. The polymerization is stopped by addition of 20 ml ofmethanol/2N hydrochloric acid (1:1). The polyethylene obtained isfiltered off and dried in an oil pump vacuum.

Activity: 857 g/(mmol·bar·h)

EXAMPLE 20

Polymerization of ethene

200 ml of toluene and 19 ml of 10.5% strength methylaluminoxane solutionin toluene are placed in a 1 l glass autoclave. 1 ml of 10.5% strengthmethylaluminoxane solution in toluene and 15 mg of bis((1′H, 1′H, 2′H,2′H-perfluorooctyl)cyclopentadienyl)zirconium dichloride are addedthereto. The polymerization temperature of 10° C. is subsequently setand the autoclave is pressurized with 2 bar of ethene; the ethenepressure is maintained during the polymerization by injection of furtheramounts. The polymerization is stopped by addition of 20 ml ofmethanol/2N hydrochloric acid (1:1). The polyethylene obtained isfiltered off and dried in an oil pump vacuum.

Activity: 600 g/(mmol·bar·h)

EXAMPLE 21

Polymerization of methyl vinyl ketone

A solution of 18 mg of bis(2′, 2′,2′-trifluoroethyl)cyclopentadienyl)dimethylzirconium and 82 mg oftris(pentafluorophenyl)borane in 20 ml of methylene chloride is cooledto 0° C. and 2 ml of methyl vinyl ketone are added. The mixture isstirred for 1 hour and then quenched by addition of ml of methanol,after which excess monomer is removed in an oil pump vacuum.

Activity: 3.8 g/(mmol·h)

We claim:
 1. A catalyst system comprising (a) at least one cocatalyst,(b) at least one organometallic compound of the formula (I)

where M¹ is a metal of group 3, 4, 5 or 6 of the Periodic Table of theElements or a lanthanide or actinide, R¹ are identical or different andare each a hydrogen atom, a C₁-C₃₀ group, SiR³, where R³ are identicalor different and are each a hydrogen atom or a C₁-C₄₀ group, or two ormore radicals R¹ may be joined to one another in such a way that theradicals R¹ and the atoms of the cyclopentadienyl ring which connectthem form a C₄-C₂₄ ring system which may in turn be substituted, R² areidentical or different and are each fluorine-containing C₁-C₂₅-alkyl orfluorine-containing C₁-C₂₅-alkenyl, r, n are identical or different andare 1, 2, 3, 4 or 5, m, q are identical or different and are 0, 1, 2, 3or 4, q+r is 5 when v=0, and q+r is 4 when v=1, m+n is 5 when v=0, andm+n is 4 when v=1, s, t are identical or different and are each aninteger from 1 to 20, L are identical or different and are each ahalogen atom or a hydrocarbon-containing radical having 1-20 carbonatoms, x is an integer from 1 to 4, with x preferably being 2 when M¹=Ti, Zr or Hf, Z is a bridging structural element between the twocyclopentadienyl rings, and v is 0 or 1, and, if desired, (c) at leastone support.
 2. A catalyst system as claimed in claim 1, wherein, in theformula (I), M¹ is titanium, zirconium or hafnium, R¹ are identical ordifferent and are each C₁-C₂₅-alkyl, C₂-C₂₅-alkenyl,C₃-C₁₅-alkylalkenyl, C₆-C₂₄-aryl, C₅-C₂₄-heteroaryl, C₇-C₃₀-arylalkyl,C₇-C₃₀-alkylaryl, C₁-C₁₂-alkoxy or SiR³, where R³ are identical ordifferent and are each C₁-C₂₀-alkyl, C₁-C₁₀-fluoroalkyl, C₁-C₁₀-alkoxy,C₆-C₂₀-aryl, C₆-C₁₀-fluoroaryl, C₆-C₁₀-aryloxy, C₂-C₁₀-alkenyl,C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl or C₈-C₄₀-arylalkenyl, L areidentical or different and are each C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₂₀-alkoxy, C₆-C₁₄-aryloxy or C₆-C₄₀-aryl.
 3. A catalyst system asclaimed in claim 1, wherein, in the formula (I), R¹ are identical ordifferent and are each methyl, ethyl, tert-butyl, cyclohexyl, octyl,pyridyl, furyl or quinolyl.
 4. A catalyst system as claimed in claim 1,wherein, in the formula (I), Z is M²R⁴R⁵, where M² is carbon, silicon,germanium or tin and R⁴ and R⁵ are identical or different and are each aC₁-C₂₀-hydrocarbon group such as C₁-C₁₀-alkyl or C₆-C₁₄-aryl.
 5. Acatalyst system as claimed in claim 1, wherein, in the formula (I), Z isCH₂, CH₂CH₂, CH(CH₃)CH₂, CH(C₄H₉)C(CH₃)₂, C(CH₃)₂, (CH₃)₂Si,(CH₃CH₂)₂Si, (CH₃)((CH₃)₃C)Si, (CH₃)₂Ge, (CH₃)₂Sn, (C₆H₅)₂Si,(C₆H₅)(CH₃)Si, (C₆H₅)₂Ge, (C₆H₅)₂Sn, (CH₂)₄Si, CH₂Si(CH₃)₂, o-C₆H₄ or2,2′-(C₆H₄)₂.
 6. A process for preparing polyolefins by polymerizationof olefins in the presence of at least one catalyst system as claimed inclaim 1.